WO1995029591A1 - Agent d'antifouling marin - Google Patents

Agent d'antifouling marin Download PDF

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Publication number
WO1995029591A1
WO1995029591A1 PCT/JP1995/000852 JP9500852W WO9529591A1 WO 1995029591 A1 WO1995029591 A1 WO 1995029591A1 JP 9500852 W JP9500852 W JP 9500852W WO 9529591 A1 WO9529591 A1 WO 9529591A1
Authority
WO
WIPO (PCT)
Prior art keywords
group
compound
acrylonitrile
chlorophenyl
phenyl
Prior art date
Application number
PCT/JP1995/000852
Other languages
English (en)
Japanese (ja)
Inventor
Hideo Okada
Atsuya Mochizuki
Hideo Ohi
Original Assignee
Ihara Chemical Industry Co., Ltd.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Ihara Chemical Industry Co., Ltd. filed Critical Ihara Chemical Industry Co., Ltd.
Priority to DE69527335T priority Critical patent/DE69527335T2/de
Priority to EP95917491A priority patent/EP0706758B1/fr
Priority to US08/564,270 priority patent/US5603755A/en
Priority to KR1019950705824A priority patent/KR100296084B1/ko
Publication of WO1995029591A1 publication Critical patent/WO1995029591A1/fr

Links

Classifications

    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
    • A01N43/74—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms five-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,3
    • A01N43/78—1,3-Thiazoles; Hydrogenated 1,3-thiazoles
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D277/00—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings
    • C07D277/02—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings
    • C07D277/20—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D277/22—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
    • C07D277/30—Radicals substituted by carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/16—Antifouling paints; Underwater paints
    • C09D5/1606—Antifouling paints; Underwater paints characterised by the anti-fouling agent
    • C09D5/1612—Non-macromolecular compounds
    • C09D5/1625—Non-macromolecular compounds organic

Definitions

  • the present invention relates to underwater structures such as equipment placed on the bottom of ships and underwater such as fishing nets and buoys, and auxiliary equipment for dams, condenser cooling water for thermal power plants, or petrochemicals.
  • the present invention relates to an antifouling agent that adheres to underwater organisms to prevent harmful underwater organisms from adhering to and propagating in the intake channels of cooling water for industrial heat exchangers.
  • Underwater structures such as underwater facilities such as ship bottoms and buoys, and auxiliary facilities for dams, etc., and constantly in contact with water for cooling water in condensers for thermal power plants or cooling water for heat exchangers in the petrochemical industry. If no treatment is applied to the fishing nets for fishing, aquaculture or fixed nets, etc. And algae adhere and propagate. These attached organisms cause an increase in fluid resistance and a decrease in thermal conductivity, leading to unfavorable conditions such as a decrease in facility functions. In addition, in the fishing nets, the above-mentioned flora and fauna adheres to the nets, blocking the mesh and causing oxygen deficiency, damaging the fish and lowering its commercial value, as well as causing fish diseases to be transmitted by bacteria.
  • an antifouling agent containing an organotin compound as an active ingredient has been used to prevent such seawater and freshwater pests from adhering and growing.
  • antifouling agents containing organotin compounds etc. contaminate the environment of rivers or the ocean, and also cause harm to humans using fish as a medium.
  • Social problems have arisen. For this reason, restrictions have been imposed on the use of organotin compounds, and both their use and production are subject to legal restrictions.
  • the present invention solves the above-mentioned problems, and provides a submerged biofouling agent containing, as an active ingredient, an organic compound having high safety, a low dose, and a high antifouling effect, other than an organotin compound.
  • the purpose is to provide.
  • the present inventors have conducted intensive studies on the antifouling activity of various organic compounds in water to achieve the above object. As a result, surprisingly, the present inventors have found that a high level of biofouling in the 3-oxopropionitrile derivative is high. Based on these findings, it was found that there is a substance having a fouling activity, and that the use of this compound can achieve the above object and provide a water-fouling biological antifouling agent having a high antifouling effect. The present invention has been completed. Disclosure of the invention
  • the present invention provides a compound represented by the general formula (1):
  • R 1 represents a lower alkyl group or a phenyl group (the phenyl group may be substituted with a halogen atom and / or a lower alkyl group)
  • XI represents a halogen atom
  • ⁇ represents 1
  • ⁇ is 2 or more
  • X 1 may be the same or different
  • ⁇ 1 is a hydrogen atom or a group ⁇ — ⁇ 2 ( ⁇ is a carbonyl group or a sulfonyl group.
  • ⁇ 2 represents an aryl group or a lower alkyl group which may be substituted.
  • X 1 is a halogen atom substituted at the 2-position and Z or 6-position, and when n is 2, X 1 May be the same or different and provide a biofouling agent attached to water wherein Y 1 is a hydrogen atom.
  • the underwater biofouling agent of the present invention (hereinafter may be simply referred to as “this agent”) is a compound represented by the general formula (1) or a salt thereof (hereinafter, including these). It may simply be referred to as “the compound of the present invention.” One or more selected from the above are contained as active ingredients.
  • This drug compound is disclosed in No. 3 or JP-A-55-154962, but it is not known to have an antifouling effect on organisms attached to water.
  • the substituent R 1 in the formula of the general formula (1) is a straight-chain, branched-chain, or lower alkyl group which may have a Z or alicyclic structure
  • lower alkyl group is synonymous with Or a lower alkyl group and a phenyl which may be substituted with Z or a halogen atom including a chlorine atom, a bromine atom, an iodine atom and a fluorine atom (hereinafter, the halogen atom is synonymous).
  • XI represents a halogen atom
  • n represents an integer of 1 to 5 (when n is 2 or more, ⁇ may be the same or different)
  • ⁇ 1 is a hydrogen atom or a group ⁇ — ⁇ 2 ( ⁇ represents a carbonyl group or a sulfonyl group, and ⁇ 2 represents an aryl group or a lower alkyl group which may be substituted) or a salt thereof.
  • ⁇ 1 is a hydrogen atom, for example,
  • Etc. can be exemplified.
  • the compound represented by the general formula (1) has the following tautomeric structure when ⁇ 1 is a hydrogen atom, but may be used as an active ingredient in the present invention at all.
  • ⁇ is a carbonyl group or a sulfonyl group
  • ⁇ 2 is an aryl group or a lower alkyl group which may be substituted. Any compound or a salt thereof may be used. Specifically, when is a carbonyl group, for example,
  • Etc. can be exemplified.
  • Z is a sulfonyl group, for example,
  • Y] in the compound represented by the general formula (1) is a hydrogen atom, for example, as shown in the following flow, the corresponding thiazolyl acetonitrile and an acid halide are used in the presence of an organic base. Thus, it can be produced by reacting in an inert solvent (see JP-A-55-154963).
  • R i, XI and n have the same meaning as described above, and A represents a halogen atom.
  • Y 1 in the compound represented by the general formula (1) is a group —Z—Y 2 , for example, as shown in the following flow, C 1—Z 1 Y It can be produced by reacting 2.
  • the salts include compounds represented by the general formula (1), for example, alkylamine, dialkylamine, trialkylamine, aniline, benzylamine, phenethylamine, ammonia, etc.
  • R 2 , R 3 , and R 4 are each independently a lower alkyl group optionally having a linear, branched, or ring structure, a phenyl group optionally having a substituent, an aralkyl group, Indicates a hydrogen atom.
  • Amines, or nitrogen-containing heterocyclic organic bases including pyridine, morpholine, piperidine, pyrrolidine, etc., each of which may have a substituent; It can be produced by reacting with a base such as an alkali metal compound such as an alkali metal hydride or an organic alkali metal compound (see Japanese Patent Publication No. 55-154962).
  • a base such as an alkali metal compound such as an alkali metal hydride or an organic alkali metal compound (see Japanese Patent Publication No. 55-154962).
  • the water-borne biofouling agent of the present invention can use the present compound itself as it is, but depending on the purpose and object, for example, forms a suitable dosage form such as a paint, a solution, an emulsion, or a pellet or flake.
  • underwater structures such as the bottom of ships, fishing nets, buoys, etc.
  • underwater structures such as dam attachments, condenser cooling water for thermal power plants, and petrochemical industry It can be used for a wide range of objects requiring antifouling organisms such as water intake channels for cooling heat exchangers.
  • the underwater biofouling antifouling agent of the present invention is installed in the bottom of a ship and in the sea, such as fishing nets and buoys; underwater structures such as dam attachments; When used in areas that are in constant contact with seawater, such as the intake channel for cooling water for industrial heat exchangers, this compound is usually formulated into a paint and used, but if desired, it can be introduced into the intake channel in the form of an emulsion. It may be added. Further, the present compound may be formed into a pellet by a method such as hot melt molding or mixed compression molding with a hydrophilic resin, a surfactant or the like, and may be placed in a cooling water system using seawater.
  • the compound of the present invention is blended with a film forming agent, if necessary, a plasticizer, a coloring pigment, an extender pigment, and other components commonly used in paint preparation.
  • the coating may be formed using a conventional dispersing machine such as a stirrer or a three-roll mill or a sand mill. That is, for example, the present compound compound and an aromatic solvent such as toluene, xylene, cumene, and naphtha, an alcohol solvent such as propanol, a ketone solvent such as methyl isobutyl ketone, and the like, if necessary.
  • Formulations can be made by blending synthetic resins such as oil varnishes and acrylic resins, synthetic rubbers, film-forming agents such as rosin, dyes, etc., and this compound and solvent, film-forming agents, octyl phthalate (DOP) , Chlorinated paraffin and other plasticizers, red pigments and other coloring pigments, or barium sulfate, talc and zinc white powder Can be used.
  • the compound of the present invention can be formulated into an emulsion by mixing water, a water-immiscible solvent such as the above-mentioned aromatic hydrocarbon, and a known surfactant such as anionic, nonionic and cationic surfactants. .
  • the compound of the present invention and, if necessary, a plasticizer and a surfactant are blended as constituents based on a hydrophilic resin such as polyethylene glycol which is solid at room temperature, and then melt molding or compression molding is performed. It can be made into pellets and flakes.
  • a hydrophilic resin such as polyethylene glycol which is solid at room temperature
  • the amount of the compound in the formulation is appropriately selected depending on the purpose, dosage form, method of use, and other conditions.There is no limit on the amount of the compound as long as the compound does not interfere with the formulation.
  • the compound of the present invention When the compound of the present invention is made into, for example, a paint, a solution, an emulsion or the like, it may be usually added at a ratio of 1 to 40% by weight, preferably 3 to 20% by weight. May be blended in a proportion of 30 to 95% by weight, preferably 50 to 90% by weight.
  • the other components may be those commonly used in each drug product, and the type, combination, blending amount, and the like are not limited to those exemplified in this specification, and may be adjusted according to desired drug properties and the like. It can be changed in a wide range as appropriate.
  • a commonly used technique such as application, spraying, impregnation, addition in water, and installation in water can be appropriately selected according to the place of use, purpose, and dosage form.
  • An effective use method is to immerse a fishing net in the underwater biofouling agent of the present invention formulated as a solution, coat and / or impregnate the fishing net, and use the same.
  • a method of adding a solution or an emulsion in water A method in which a ret or flake is used by a known installation method appropriately selected depending on the actual use situation, such as hanging or attaching, for example, can also be exemplified. Further, for example, by incorporating the present compound into the rope or fiber material used in a fishing net or the like at the manufacturing stage, and imparting the water or biocontrol ability to the rope or the fiber material itself with a dosage form and a method other than those exemplified above. Can also be used.
  • the present compound which is an active ingredient of the antifouling agent for water-borne organisms of the present invention, is particularly effective for the antifouling of animal-borne organisms. It is also useful to use it in combination with other chemicals, and in order to further improve the antifouling effect and antifouling period, there is no problem even when used in combination with other organic drugs.
  • Organic agents that can be used for these purposes include, for example, substituted phenylmaleimides, such as 2,3-diclo-N—2,6,6′-getylphenylmaleimide, and 2,4,6-trichloromethyl phenylmaleimide , Tetramethylthiuram disulphide, tetramethylthiuram disulphide, zinc dimethyldithiocarbamate, zidinbis (dimethyldithiocarbamate), ethylenebis (dithiophene), tetrachloroisophthalonitrile, 2- Thiocyanomethylthiobenzothiazole, 3,4-dichlorophenylisothiocyanate, 4,5-dichloromouth, 2-n-octyl-3- (2H) isothiazolone, 3- (3,4 —Dichlorophenyl) — 1,1-Dimethylperyl (DC MU), 2-Methylthio—4—t—Butylamino-1 6-cyclopropy
  • the biofouling agent of the present invention may be used in combination with a copper compound, for example, cuprous oxide, copper rhodan, or the like. It is only necessary to use a paint such as silicone resin or silicone oil.
  • the compound of the present invention used as an active ingredient of the antifouling agent for biofouling in water of the present invention has high safety.
  • one of the compounds of the present invention 3- (2-chlorophenyl) -1-2_ (4-phenylene Lou 2, 3 Jihidorochiazo one Roux 2- ylidene) - 3- Okisopuropio nitrile LD 5 0 values 5000 mgZK g in rats acute oral toxicity study [hereinafter test compound in test example 2 to]
  • test compound in test example 2 to thus, the mutagenicity test is negative.
  • the present invention will be described more specifically with reference to Test Examples and Formulation Examples, but the present invention is not limited to these Test Examples and Formulation Examples. Synthesis of this drug compound 1
  • TBTO Bis (tributyltin) oxide
  • Test Example 8 is a test using a dimethylamine salt
  • Test Example 9 is a test using a dihexylamine salt
  • Test Example 0 is a test using a dibutylamine salt.
  • Test Example 1 The components including the present compound used in Test Example 1 were blended in the proportions shown in Table 2 below and dispersed to 50 microns using a small laboratory atritor to obtain a biofouling agent that adheres to water as a paint.
  • the components including the present compound [the one used in Test Example 17 to be described later] were blended in the following proportions, dispersed and dissolved to obtain a biofouling agent that adheres to water as a solution.
  • This agent compound 70% by weight
  • Each component including the compound of the present invention [the one used in Test Example 2] was prepared in the following proportions, polyethylene glycol was dissolved, and the compound of the present invention was dispersed in this, and then molded into pellets. Was obtained.
  • Test Example 1 1 Anti-fouling effect in field immersion test
  • test plates were prepared. This test plate was fitted into an iron frame, suspended from seawater from a raft for immersion, and maintained at a depth of 1.5 m. The test plates immersed in seawater were pulled up every 1, 3 and 6 months to observe the status of the attached organisms. Table 3 shows the results. The status of the adherent organisms was indicated as follows.
  • Test Example 12 Adhesion area 30% or more Test Example 12 (Anti-fouling effect in field immersion test) An underwater immersion test was performed in the same manner as in Test Example 11 except that the drug substance compound in the biofouling agent that adheres to water in water was changed from that used in Test Example 1 to that used in Test Example 2. Table 3 shows the results. The status of the attached organisms was evaluated and displayed in the same manner as in Test Example 11.
  • a submerged immersion test was performed in the same manner as in Test Example 11 except that an FRP plate to which no underwater biofouling agent was applied was used as a test plate. The results are shown in Table 3. The attached state of the attached organisms was evaluated and displayed in the same manner as in Test Example 11.
  • the biofouling antifouling agent in water according to the present invention contains a compound other than the organotin compound as an active ingredient, and has high safety and a low content of fouling organisms on ships, underwater structures, fishing nets and the like. It has a long-term stable antifouling effect.

Abstract

L'invention concerne un agent d'antifouling marin contenant un composé représenté par la formule générale (1) et/ou un sel de celui-ci comme ingrédient actif. Dans ladite formule (I), R1 représente un groupe alkyle inférieur ou un groupe phényle pouvant être remplacé par un atome d'halogène et/ou un groupe alkyle inférieur; X1 représente un atome d'halogène; n représente un nombre entier compris entre 1 et 5, à condition que lorsque n représente 2 ou plus, les X puissent être identiques ou différents; Y1 représente un atome d'hydrogène ou un groupe-Z-Y2; Z représente un groupe carbonyle ou sulfonyle; et Y2 représente un groupe aryle facultativement substitué ou bien un groupe alkyle inférieur. Cet agent est sans danger du fait de l'utilisation de l'ingrédient actif comprenant un composé autre que des composés d'organotine, il empêche le dépôt d'organismes marins sur la coque de bateaux, des constructions sous-marines, des filets de pêche et ainsi de suite, même en une faible dose, et il présente un effet antifouling stable durable.
PCT/JP1995/000852 1994-04-28 1995-04-28 Agent d'antifouling marin WO1995029591A1 (fr)

Priority Applications (4)

Application Number Priority Date Filing Date Title
DE69527335T DE69527335T2 (de) 1994-04-28 1995-04-28 Mittel gegen den bewuchs durch meeresorganismen
EP95917491A EP0706758B1 (fr) 1994-04-28 1995-04-28 Agent d'antifouling marin
US08/564,270 US5603755A (en) 1994-04-28 1995-04-28 Preventive agent for fouling organisms
KR1019950705824A KR100296084B1 (ko) 1994-04-28 1995-04-28 수중부착생물방오제

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP11461794A JP3404558B2 (ja) 1994-04-28 1994-04-28 水中付着生物防汚剤
JP6/114617 1994-04-28

Publications (1)

Publication Number Publication Date
WO1995029591A1 true WO1995029591A1 (fr) 1995-11-09

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ID=14642347

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP1995/000852 WO1995029591A1 (fr) 1994-04-28 1995-04-28 Agent d'antifouling marin

Country Status (8)

Country Link
US (2) US5603755A (fr)
EP (1) EP0706758B1 (fr)
JP (1) JP3404558B2 (fr)
KR (1) KR100296084B1 (fr)
DE (1) DE69527335T2 (fr)
ES (1) ES2179873T3 (fr)
TW (1) TW295576B (fr)
WO (1) WO1995029591A1 (fr)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1998042683A1 (fr) * 1997-03-21 1998-10-01 Nippon Soda Co., Ltd. Composes de triazole, leur procede de preparation, et insecticides et acaricides
US6063734A (en) * 1996-04-25 2000-05-16 Nissan Chemical Industries, Ltd. Etylene derivatives and pesticides containing said derivatives
US6642234B1 (en) 1998-12-25 2003-11-04 Nissan Chemical Industries, Ltd. Acrylonitrile compounds
EP1114820A4 (fr) * 1998-09-17 2005-01-19 Nippon Soda Co Thiazolylcinnamonitriles et agents antiparasitaires

Families Citing this family (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AU5514896A (en) * 1995-04-27 1996-11-18 Nissan Chemical Industries Ltd. Oxopropionitrile derivatives and insect rest control agents
CA2286131A1 (fr) * 1997-04-11 1998-10-22 Janssen Pharmaceutica, N.V. Compositions de revetement a base de busoxinone
EP1110454A3 (fr) * 1999-12-16 2002-06-05 Rohm And Haas Company 5-Carboxanilido-haloalkylthiazoles comme agents antimicrobiens et anti-salissures marines
AU2001241170A1 (en) * 2000-03-17 2001-09-24 Nippon Soda Co., Ltd. Acrylonitrile compounds and pest controllers
US6410622B1 (en) 2000-09-11 2002-06-25 Gregory W. Endres Method of preventing fouling organisms in marine environments and polymer-bound nitric oxide/nitric oxide-releasing compositions usable therefor
CN1561335A (zh) * 2001-10-02 2005-01-05 日本曹达株式会社 乙烯衍生物的制备方法
US20060002234A1 (en) * 2004-06-30 2006-01-05 Lobe Henry J Anti-biofouling seismic streamer casing and method of manufacture
KR100876985B1 (ko) * 2008-04-07 2009-01-07 듀라케미 (주) 해양생물 미부착 방오층이 형성된 해양 및 항만구조물 및그 방오층의 형성방법

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JPS5070524A (fr) * 1973-10-25 1975-06-12
JPS55154962A (en) * 1979-05-17 1980-12-02 Schering Ag Salt of thiazolilideneeoxoopropionitrile* its manufacture* insecticide containing it and method of converting said thiazolilideneeoxoo propionitrile alkali metal salt to other derivative
JPS61180778A (ja) * 1985-02-01 1986-08-13 シエル・インターナシヨネイル・リサーチ・マーチヤツピイ・ベー・ウイ １、３―チアゾール誘導体、それらの製造方法および殺虫組成物

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DE2703542C2 (de) * 1977-01-26 1985-09-26 Schering AG, 1000 Berlin und 4709 Bergkamen Thiazolylzimtsäurenitrile, Insektenbekämpfungsmittel enthaltend diese Verbindungen sowie Verfahren zu ihrer Herstellung

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JPS5070524A (fr) * 1973-10-25 1975-06-12
JPS55154962A (en) * 1979-05-17 1980-12-02 Schering Ag Salt of thiazolilideneeoxoopropionitrile* its manufacture* insecticide containing it and method of converting said thiazolilideneeoxoo propionitrile alkali metal salt to other derivative
JPS61180778A (ja) * 1985-02-01 1986-08-13 シエル・インターナシヨネイル・リサーチ・マーチヤツピイ・ベー・ウイ １、３―チアゾール誘導体、それらの製造方法および殺虫組成物

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6063734A (en) * 1996-04-25 2000-05-16 Nissan Chemical Industries, Ltd. Etylene derivatives and pesticides containing said derivatives
US6462049B1 (en) 1996-04-25 2002-10-08 Nissan Chemical Industries, Ltd. Ethylene derivatives and pesticides containing said derivatives
USRE38188E1 (en) 1996-04-25 2003-07-15 Nissan Chemical Industries, Ltd. Ethylene derivatives and pesticides containing said derivatives
US7037880B2 (en) 1996-04-25 2006-05-02 Nissan Chemical Industries, Ltd. Ethylene derivatives and pesticides containing said derivatives
US7566683B2 (en) 1996-04-25 2009-07-28 Nissan Chemical Industries, Ltd. Ethylene derivatives and pesticides containing said derivatives
WO1998042683A1 (fr) * 1997-03-21 1998-10-01 Nippon Soda Co., Ltd. Composes de triazole, leur procede de preparation, et insecticides et acaricides
EP1114820A4 (fr) * 1998-09-17 2005-01-19 Nippon Soda Co Thiazolylcinnamonitriles et agents antiparasitaires
US6642234B1 (en) 1998-12-25 2003-11-04 Nissan Chemical Industries, Ltd. Acrylonitrile compounds

Also Published As

Publication number Publication date
ES2179873T3 (es) 2003-02-01
JP3404558B2 (ja) 2003-05-12
EP0706758A1 (fr) 1996-04-17
EP0706758B1 (fr) 2002-07-10
DE69527335D1 (de) 2002-08-14
JPH07300402A (ja) 1995-11-14
US5603755A (en) 1997-02-18
EP0706758A4 (fr) 1998-08-12
KR100296084B1 (ko) 2001-11-30
KR960702985A (ko) 1996-06-19
TW295576B (fr) 1997-01-11
DE69527335T2 (de) 2002-11-14
US5658375A (en) 1997-08-19

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